JP2008517107A - Secondary and tertiary amines as friction modifiers for automatic transmission fluids - Google Patents

Abstract

A major amount of oil of lubricating viscosity; a secondary or tertiary amine represented by R ¹ R ² NR ³ , wherein R ¹ and R ² are alkyl groups of at least 6 carbon atoms, and R ³ is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group); and the dispersant composition, particularly as a friction component of an automatic transmission, during oxidative and mechanical stress application Provides a high static friction coefficient and a durable positive slope.

Description

(Background of the Invention)
The present invention relates to fluid additives such as automatic transmission oil, traction oil, continuously variable transmission (CVT) oil, dual clutch automatic transmission oil, agricultural tractor oil, and engine lubricant.

  In the market for automatic transmissions, the desire to increase transmission capacity while reducing weight has led to rapid engine changes that show a high coefficient of static friction with improved clutch retention. Automatic transmission fluid is desired. At the same time, it is desirable to improve the retention of positive slope characteristics in the μ / v (friction coefficient vs. sliding speed) curve. There are new tests in the market that are used to define these properties. The static torque can be measured with a test such as the Toyota SAE # 2 friction test, and the retention of the positive slope can be measured with a procedure such as JASO LVFA (Japan Automatic Standards Organization, Low Velocity Friction Apparatus). The μ / v slope is measured periodically during oxidative and mechanical aging.

  There are patents that describe the friction modifier technology used to achieve this performance (e.g., Patent Document 1). The requirement of combining a high static coefficient of friction with a durable positive slope is often incompatible with traditional ATF friction modifier technology, which is described in great detail in this patent document. Many of the commonly used friction modifiers have a low coefficient of static friction and do not have a positive slope that is durable enough to withstand satisfactory use. Another patent document describing a technique that retains positive mu / v or anti-shudder properties includes US Pat. These may use a combination of metal detergent and friction modifier.

  U.S. Patent No. 6,099,017 (Adams et al., Jan. 22, 2004) describes (a) a friction modifier derived from the reaction of a carboxylic acid with an aminoalcohol (this friction modifier contains at least two hydrocarbyl groups. ), And (b) a dispersant composition, which provides good friction properties in an automatic transmission.

  U.S. Patent No. 6,057,031 discloses lubricating oils containing various products, which can be various imidazolines or oxazolines of the following structure:

ここで、Ｒ_２およびＲ_３は、それぞれ、ＣＨ_２ＯＣＯＲ_１、ＣＨ_２ＯＨまたはＨを表わし、これらの生成物は、カルボン酸（またはその反応性誘導体）とアミノアルコールの縮合（例えば、２モルのイソステアリン酸と１モルのトリス−ヒドロキシメチルアミノメタン（ＴＨＡＭ）との縮合）により、調製される。
米国特許第５，７５０，４７６号明細書 米国特許第５，８５８，９２９号明細書 国際公開第０４／００７６５２号パンフレット 米国特許第４，８８６，６１２号明細書

Here, R ₂ and R ₃ each represent CH ₂ OCOR ₁ , CH ₂ OH or H, and these products are a condensation of a carboxylic acid (or a reactive derivative thereof) and an amino alcohol (for example 2 mol Of isostearic acid and 1 mol of tris-hydroxymethylaminomethane (THAM)).
US Pat. No. 5,750,476 US Pat. No. 5,858,929 International Publication No. 04/007652 Pamphlet US Pat. No. 4,886,612

  The present invention provides a high coefficient of static friction and maintains a durable positive slope, especially during oxidative and mechanical stressing of the friction system, for use in automatic transmissions. To solve this problem, a new and relatively simple and inexpensive friction modifier is developed. This is accomplished by using a friction modifier containing a secondary or tertiary amine having at least 2 alkyl groups of at least 6 carbon atoms, as described further below.

(Summary of the Invention)
The present invention provides a composition suitable for lubricating a transmission, the composition comprising:
(A) a major amount of oil of lubricating viscosity;
(B) Secondary or tertiary amine represented by the following formula: R ¹ R ² NR ³
Wherein R ¹ and R ² are each independently an alkyl group of at least 6 carbon atoms and R ³ is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group; and (C) Dispersant.

  The present invention further provides a method of lubricating a transmission, the method comprising supplying the composition thereto.

  The present invention further provides a concentrate suitable for dilution with oil of lubricating viscosity to prepare a lubricant for a transmission, the concentrate comprising: (a) the concentrate Forming oils of lubricating viscosity; (b) secondary or tertiary as described above; and (c) dispersants.

(Detailed description of the invention)
Various preferred features and embodiments are described below by way of non-limiting examples.

  One component of the present invention is an oil of lubricating viscosity, which can be present in a major amount in the lubricating composition and in a concentrate forming amount in the concentrate. Suitable oils include natural and synthetic lubricating oils and mixtures thereof. In fully formulated lubricants, this oil of lubricating viscosity is generally present in a major amount (ie, greater than 50% by weight). Typically, the oil of lubricating viscosity is present in an amount from 75 to 95%, often greater than 80% by weight of the composition.

  Natural oils useful in producing the lubricants and hydraulic fluids of the present invention include not only animal and vegetable oils, but also mineral lubricating oils (e.g., liquid petroleum oils, and paraffinic, naphthenic or mixed paraffins). Naphthenic and solvent-treated mineral or acid-treated mineral lubricants; these can be further refined by hydrocracking and hydrofinishing processes).

Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils (eg, polymerized olefins and interpolymerized olefins (also known as polyalphaolefins); polyphenyls; alkylated diphenyl ethers; Alkyl- or dialkylbenzenes; and alkylated diphenyl sulfides; and their derivatives, analogs and homologues). Further, alkylene oxide polymers and derivatives thereof (in this derivative, the terminal hydroxyl group can be modified by esterification or etherification) are also included. Also, esters of dicarboxylic acids with variety of alcohols or C ₅ -C ₁₂ esters prepared from monocarboxylic acids and polyols or polyol ethers, are also included. Other synthetic oils include silicon base oils, liquid esters of phosphorus-containing acids, and polymeric tetrahydrofuran.

  Unrefined oils, refined oils and rerefined oils (which are either natural or synthetic oils of the type disclosed above, and mixtures of any two or more thereof) Can be used in lubricants. Unrefined oil is obtained directly from natural or synthetic raw materials without further purification. The refined oil was further processed in one or more purification steps to improve one or more properties. They can be hydrogenated, for example, to obtain oils of lubricating viscosity with improved stability to oxidation.

  In one embodiment, the oil of lubricating viscosity is an API Group II, Group III, Group IV or Group IV oil (including synthetic oils or mixtures thereof). These are classifications established by the API Base Oil Interchangeability Guidelines. Both Group II and Group III oils contain <0.03 percent sulfur and> 99 percent saturates. Group II oils have a viscosity index of 80-120, and Group III oils have a viscosity index of> 120. Polyalphaolefins are classified as Group IV. The oil can also be an oil derived from hydroisomerization of a wax such as slack wax or Fischer-Tropsch synthetic wax. Group V excludes "all others" (Group I, which contains> 0.03% S and / or <90% saturates and has a viscosity index of 80-120) Include).

In a preferred embodiment, at least 50% by weight of the oil of lubricating viscosity is polyalphaolefin (PAO). Typically, these polyalphaolefins are derived from monomers having 4 to 30, or 4 to 20, or 6 to 16 carbon atoms. Examples of useful PAOs include those derived from 1-decene. These PAOs may have a viscosity of 1.5 to 150 mm ² / s (cSt) at 100 ° C. PAO is typically a hydrogenated material.

The oils of the present invention can include a single viscosity range oil or a mixture of high and low viscosity range oils. In a preferred embodiment, the oil exhibits a kinematic viscosity at 100 ° C. of 1 or 2-8 or 10 mm ² / sec (cSt). This overall lubricating composition preferably has a viscosity of 1 or 1.5 to 10 or 15 or 20 mm ² / sec at 100 ° C. and a Brookfield (ASTM-D-2983) at −40 ° C. of 20 Or 15 Pa-s (20,000 cP or 15,000 cP), preferably less than 10 Pa-s and even less than 5 Pa-s, formulated using oil and other ingredients.

Component (b) is a secondary or tertiary amine, which can act as a friction modifier. The amine contains at least two substituent hydrocarbyl groups (eg, alkyl groups). This amine is represented by the following formula:
R ¹ R ² NR ³
Where R ¹ and R ² are each independently an alkyl group of at least 6 carbon atoms (eg, 8-20, or 10-18 or 12-16 carbon atoms); R ³ is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group. A commercially available example of such an amine is Armeen 2C ™, which is believed to have two C ₁₂ alkyl groups.

In one embodiment, the amine comprises a di-cocoalkylamine or a homologous amine. Di - cocoalkyl amine (or di - cocoamine) comprises two mainly C ₁₂ groups R groups in the above formula (which is derived from coconut oil), and and the remaining R groups are H Secondary amine.

In another embodiment, R ³ of the above structure is —CH ₂ —CHOH—R ⁴ , wherein R ⁴ is hydrogen or an alkyl group (eg, a methyl group, or 1 to 26 carbon atoms). Or an alkyl group of 6 to 20 carbon atoms, or 12 to 18 carbon atoms, or 14 to 16 carbon atoms, or 14 carbon atoms). Such materials can be prepared by reaction of a secondary amine (eg, di-cocoalkylamine) and an epoxide (eg, propylene oxide (when R ⁴ is methyl)). The resulting product can therefore be more specifically represented by the following structure:
R ¹ R ² N—CH ₂ —CHOH—CH ₃
Here, R ¹ and R ² are independently alkyl groups of 8 to 20 carbon atoms, as described above. The reaction between the dialkylamine and the epoxide can be triggered under pressure and in the presence of a basic catalyst. In another embodiment, R ³ is an aminopropyl group (eg, —CH ₂ —CH ₂ —CH ₂ —NH ₂ ) and the resulting product is a secondary amine (eg, dicocoalkyl). Amine) and acrylonitrile followed by reduction.

  The amount of component (b) in the composition of the present invention generally reduces the shudder in an automatic transmission (ie, performance deficiencies observed during shifting when the balance of the friction characteristics of the transmission oil is insufficient). An amount appropriate to prevent or reduce. An effective amount can be 0.01 to 10.0 weight percent of the finished fluid formulation. Alternative amounts include 0.02 to 5 percent, or 0.1 to 3 percent, or 0.1 to 2 percent, or 0.5 to 1.5 percent. In concentrates, these amounts increase proportionally.

  Component (c) is a dispersant. It can be described as "other than the species of (b)" if some of the friction modifiers of (b) can exhibit some dispersant properties. Examples of “carboxylic acid dispersants” are described in a number of US patents including: 3,219,666, 3,316,177, 3,340,281, 3, 351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542 No. 680, No. 3,576,743, No. 3,632,511, No. 4,234,435, No. 26,433, and No. 6,165,235.

Succinimide dispersants are one type of carboxylic acid dispersant, but they react hydrocarbyl-substituted succinic anhydrides (or their reactive equivalents (eg, acids, acid halides or esters)) with the amines described above. To be prepared. The hydrocarbyl substituent contains, on average, at least 8, or 20, or 30, or 35 to 350, or 200, or 100 carbon atoms. In one embodiment, the hydrocarbyl group is derived from a polyalkene. Such polyalkenes can be characterized by an M _n (number average molecular weight) of at least 500. In general, the polyalkene is characterized by a M _n of 500, or 700, or 800, or 900 to 5000, or 2500, or 2000, or 1500. In other embodiments, M _n varies from 500, or 700, or 800 to 1200, or 1300. In one embodiment, the polydispersity (M _w / M _n ) is at least 1.5.

  These polyalkenes include homopolymers and interpolymers having 2 to 16, or 6 or 4 carbon atoms. These olefins are monoolefins (eg, ethylene, propylene, 1-butene, isobutene and 1-octene); or polyolefinic monomers (eg, diolefinic monomers (eg, 1,3-butadiene and isoprene)). obtain. An example of a polymer is polybutene. In some cases, about 50% of the polybutene is derived from isobutylene. These polyalkenes can be prepared by conventional procedures.

  In one embodiment, these succinic acylating agents are prepared by reacting a polyalkene with an excess of maleic anhydride to provide a substituted succinic acylating agent, where for each equivalent of substituents. The number of succinic groups is at least 1.3, for example 1.5, or 1.7, or 1.8. The maximum number of succinic groups per substituent does not exceed 4.5, or 2.5, or 2.1, or 2.0. The preparation of substituted succinic acylating agents whose substituents are derived from such polyolefins is described in US Pat. No. 4,234,435.

  The substituted succinic acylating agent can react with amines (including the amines above) and heavy amine products (known as amine stationary bottoms). The amount of amine reacted with the acylating agent is typically that which produces a CO: N molar ratio of 1: 2 to 1: 0.75. If the amine is a primary amine, complete condensation to the imide can occur. Varying amounts of amine product (eg, amic acid) may also be present. If this reaction is rather with an alcohol, the resulting dispersant is an ester dispersant. If both an amine function and an alcohol function are present, whether it is a separate molecule or the same molecule (like the condensed amine above), the mixture of amide, ester and possibly imide functions Can exist. These are so-called ester-amide dispersants.

  An “amine dispersant” is a reaction product of a relatively high molecular weight aliphatic or alicyclic halide and an amine (preferably a polyalkylene polyamine). Examples thereof are described, for example, in the following US patents: 3,275,554, 3,438,757, 3,454,555, and 3,565,804.

  “Mannich dispersants” are reaction products of alkylphenols whose alkyl groups contain at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially amine condensates and polyalkylene polyamines). The materials described in the following US patents are exemplary: 3,036,003, 3,236,770, 3,414,347, 3,448,047, 3,461. 172, 3,539,633, 3,586,629, 3,591,598, 3,634,515, 3,725,480, 3,726,882 No., and 3,980,569.

  “Post-treatment dispersants” are also part of the present invention. They are obtained by post-treating carboxylic acid dispersants, amine dispersants or Mannich dispersants with reagents such as: urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon substitutions. Succinic anhydride, nitriles, epoxides, boron-containing compounds (eg, boric acid (to produce a “borateized dispersant”), phosphorus-containing compounds (eg, phosphorus-containing acids or anhydrides), or 2,5-di Mercaptothiadiazole (DMTD), etc. Representative materials of this type are described in the following US patents: 3,200,107, 3,282,955, 3,367,943, 3,513,093, 3,639,242, 3,649,659, 3,442,808, 3,455,832, 3,579, No. 50, No. 3,600,372, No. 3,702,757, and No. 3,708,422.

  Mixtures of dispersants can also be used.

  The amount of component (c) in the composition of the present invention is generally from 0.3 to 10 weight percent. In other embodiments, the amount of component (c) is 0.5-7 percent or 1-5 percent of the blended final fluid formulation. In concentrates, these amounts increase proportionally.

  Other components commonly used in transmission oils (especially automatic transmission oils (ATF)) are also typically present.

  One component that is often used is a viscosity modifier. Viscosity modifiers (VM) and dispersant viscosity modifiers (DVM) are well known. Examples of VMs and DVMs include polymethacrylates, polyacrylates, polyolefins, styrene-maleic acid ester copolymers, and similar polymeric materials (including homopolymers, copolymers and graft polymers).

  Examples of commercially available VMs, DVMs and their chemical types include: polyisobutylene (eg, Indopol ™ from BP Amoco or Parapol ™ from ExxonMobil); olefin copolymers (eg, Lubrizol 7060, 7065 and 7067 from Lubrizol and Trirene ™ CP-40 and CP-60 from Uniroyal; hydrogenated styrene-diene copolymers (eg, Shellivis ™ 40 and 50 from Shell, and Lubrizol) Styrene / maleate copolymers (which are dispersant copolymers) (eg LZ® 3702, 2751 from Lubrizol). And 3703); polymethacrylates, some of which have dispersive properties (eg, those of the Acryloid ™ and Viscoplex ™ series from RohMax, the TLA ™ series from Texaco, and Lubrizol) LZ 7702 ™ and LZ 7720 ™); olefin-graft-polymethacrylate polymers (eg, Viscoplex ™ 2-500 and 2-600 from Rohm GmbH); and hydrogenated polyprene star polymers (eg Shellvis ™ 200 and 260 from Shell). A recent summary of viscosity modifiers can be found in US Pat. Nos. 5,157,088, 5,256,752 and 5,395,539. These VMs and / or DVMs are incorporated into fully formulated compositions at levels up to 15% by weight. Preferred amounts are 1-12% or 3-10%.

Another ingredient that may be used in the composition used in the present invention is an auxiliary friction modifier. Friction modifiers are well known to those skilled in the art. A useful list of friction modifiers is contained in US Pat. No. 4,792,410. US Pat. No. 5,110,488 discloses fatty acid metal salts (particularly zinc salts) useful as friction modifiers. The list of friction modifiers includes the following:
(I) Fatty phosphite ester (ii) Fatty acid amide (iii) Fatty epoxide (iv) Borated fatty epoxide (v) Fatty amines other than the above component (b) (vi) Glycerol ester (vii) Borated glycerol Esters (viii) Alkoxylated fatty amines (ix) Borated alkoxylated fatty amines (x) Metal salts of fatty acids (xi) Sulfurized olefins (xii) Fatty imidazolines (xiii) Condensation products of carboxylic acids and polyalkylene polyamines xiv) metal salts of alkyl salicylates (xv) amine salts of alkyl phosphates and mixtures thereof.

Representatives of each of these types of friction modifiers are known and commercially available. For example, (i) a fatty phosphite generally has the formula (RO) ₂ PHO. Preferred dialkyl phosphites are typically present with a small amount of monoalkyl phosphite of formula (RO) (HO) PHO, as shown in the previous formula. In these structures, the term “R” is conveniently referred to as an alkyl group. Of course, this alkyl is in fact alkenyl, and thus the terms “alkyl” and “alkylation” as used herein encompass other than saturated alkyl groups within the phosphate ester. Is possible. The phosphite should have sufficient hydrocarbyl groups to make the phosphite substantially lipophilic. Preferably, the hydrocarbyl group is not substantially branched. Many suitable phosphites are commercially available and can be synthesized as described in US Pat. No. 4,752,416. The phosphite preferably contains 8 to 24 carbon atoms in each of the R groups. Preferably, the fatty phosphite contains 12 to 22 carbon atoms, more preferably 16 to 20 carbon atoms, in the fatty radical. In one embodiment, the fatty phosphite may be formed from an oleyl group and thus has 18 carbon atoms in each fatty radical.

  (Iv) Borated fatty epoxides are known from Canadian Patent 1,188,704. These oil-soluble boron-containing compositions are prepared by reacting at least one boric acid or boron trioxide with at least one fatty epoxide having the following formula at a temperature of 80 ° C. to 250 ° C .:

ここで、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４の各々は、水素または脂肪族ラジカルであるか、それらのいずれか２個は、それらが結合するエポキシ炭素原子と一緒になって、環状ラジカルを形成する。この脂肪エポキシドは、好ましくは、少なくとも８個の炭素原子を含有する。

Where each of R ¹ , R ² , R ³ and R ⁴ is hydrogen or an aliphatic radical, or any two of them, together with the epoxy carbon atom to which they are attached, form a cyclic radical Form. The fatty epoxide preferably contains at least 8 carbon atoms.

These borated fatty epoxides can be characterized by their method of preparation involving the reaction of two substances. Reagent A can be either boron trioxide or various forms of boric acid including: metaboric acid (HBO ₂ ), orthoboric acid (H ₃ BO ₃ ) and tetraboric acid (H ₂ B ₄ O _7). ). Boric acid, especially orthoboric acid is preferred. Reagent B can be at least one fatty epoxide having the above formula. In this formula, each of these R groups is most often hydrogen, an aliphatic radical having at least one hydrocarbyl, or an aliphatic radical having at least 6 carbon atoms. The molar ratio of Reagent A and Reagent B is generally 1: 0.25 to 1: 4. 1: 1 to 1: 3 are preferred, and about 1: 2 is a particularly preferred ratio. The borated fatty epoxide is simply obtained by blending the two reagents and heating at 80-250 ° C., preferably 100-200 ° C., for a period sufficient to cause the reaction, Can be prepared. If desired, this reaction can occur in the presence of a substantially inert, usually liquid organic diluent. During this reaction, water is generated and can be removed by distillation.

  (Iii) The non-borated fatty epoxide corresponds to the “reagent B”, but is also useful as a friction modifier.

  Borated amines are generally known from US Pat. No. 4,622,158. Borated amine friction modifiers (including (ix) borated alkoxylated fatty amines) are conveniently prepared by reaction of the boron-containing compound with the corresponding amine. The amine can be a simple fatty amine or a hydroxy-containing tertiary amine. These borated amines can be obtained by adding the boron-containing reactant to the amine reactant and stirring the resulting mixture at 50-300 ° C., preferably 100-250 ° C. or 150 ° C.- It can be prepared by heating at 230 ° C. The reaction is continued until no by-product water is generated from the reaction mixture (this indicates completion of the reaction).

  Useful amines in preparing these borated amines include commercially available alkoxylated fatty amines known under the trademark “ETHOMEEN”, which are available from Akzo Nobel. Representative examples of these ETHOMEEN® materials include ETHOMEEN® C / 12 (bis [2-hydroxyethyl] cocoamine); ETHOMEEN® C / 20 (polyethylene [10] cocoamine); ETHOMEEN (Registered trademark) S / 12 (bis [2-hydroxyethyl] soyamin); ETHOMEEN® T / 12 (bis [2-hydroxyethyl] -taromine); ETHOMEEN® T / 15 (polyethylene- [ 5] taroamine); ETHOMEEN® 0/12 (bis [2-hydroxyethyl] oleylamine); ETHOMEEN® 18/12 (bis [2-hydroxyethyl] octadecylamine); and ETHOMEEN® 18 / 25 (Polyoki Ethylene [15] octadecylamine). Fatty amines and ethoxylated fatty amines are also described in US Pat. No. 4,741,848.

  The (viii) alkoxylated fatty amine and (v) the fatty amine itself (eg, oleylamine) are generally useful as friction modifiers in the present invention. Such amines are commercially available.

  Both borated and non-borated fatty acid esters of glycerol can be used as friction modifiers. (Vii) A borated fatty ester of glycerol is prepared by borated a fatty acid ester of glycerol with boric acid while removing the water of reaction. Preferably, there is sufficient boron to react with each of the 1.5 to 2.5 hydroxyl groups present in the reaction mixture. This reaction can be carried out in the presence or absence of any suitable organic solvent (eg, methanol, benzene, xylene, toluene or oil) at a temperature in the range of 60-135 ° C.

(Vi) The fatty acid ester of glycerol itself can be prepared by various methods well known in the art. Many of these esters (eg, glycerol monooleate and glycerol taloate) are produced on a commercial scale. Useful esters are oil soluble, preferably, C ₈ -C ₂₂ fatty acids or mixtures thereof (e.g., those found in natural products, and following those described in detail) is prepared from. Although fatty acid monoesters of glycerol are preferred, mixtures of monoesters and diesters can be used. For example, commercially available glycerol monooleate may contain 45% to 55% by weight monoester and 55% to 45% diester.

Fatty acids can be used in preparing the above glycerol esters; they can also be used in preparing (x) metal salts, (ii) amides and (xii) imidazolines, any of which are also frictional Can be used as a regulator. Preferred fatty acids include those containing 6 to 24 carbon atoms, preferably 8 to 18 carbon atoms. These acids can be branched or linear, saturated or unsaturated. Suitable acids include 2-ethylhexanoic acid, decanoic acid, oleic acid, stearic acid, isostearic acid, palmitic acid, myristic acid, palmitoleic acid, linoleic acid, lauric acid and linolenic acid, and the following natural products: Acids include: tallow, palm oil, olive oil, peanut oil, corn oil and beef foot oil. A particularly preferred acid is oleic acid. Preferred metal salts include zinc salts and calcium salts. Examples include overbased calcium salts and basic zinc oleate complex, which can be represented by Zn ₄ oleate ₃ O ₁ . Preferred amides are those prepared by condensation of ammonia with primary or secondary amines (eg, diethylamine and diethanolamine). Fatty imidazolines are condensation products of acids and diamines or polyamines (eg, polyethylene polyamines). These imidazolines are generally represented by the following structure:

ここで、Ｒは、アルキル基であり、そしてＲ’は、水素またはヒドロカルビル基または置換ヒドロカルビル基（−（ＣＨ_２ＣＨ_２ＮＨ）ｎ−基を含めて）である。好ましい実施態様では、この摩擦調整剤は、Ｃ_８〜Ｃ_２４脂肪酸とポリアルキレンポリアミンとの縮合生成物、特に、イソステアリン酸とテトラエチレンペンタミンとの生成物である。カルボン酸およびポリアルキレンアミン（ｘｉｉｉ）の縮合生成物は、一般に、イミダゾリンまたはアミドであり得る。

Here, R is an alkyl group, and R ′ is hydrogen or a hydrocarbyl group or a substituted hydrocarbyl group (including a — (CH ₂ CH ₂ NH) n— group). In a preferred embodiment, the friction modifier is the condensation product of a C ₈ -C ₂₄ fatty acid with a polyalkylene polyamine, especially a product of isostearic acid with tetraethylenepentamine. The condensation product of carboxylic acid and polyalkyleneamine (xiii) can generally be an imidazoline or amide.

  Sulfurized olefin (xi) is a well-known commercial material used as a friction modifier. Particularly preferred sulfurized olefins are those prepared according to the detailed teachings of US Pat. Nos. 4,957,651 and 4,959,168. Here, a co-sulfided mixture of two or more reactants selected from the group consisting of: (1) at least one fatty acid ester of a polyhydric alcohol, (2) at least one species. (3) at least one olefin, and (4) at least one fatty acid ester of a monohydric alcohol.

  The reactant (3), the olefin component, contains at least one olefin. The olefin is preferably an aliphatic olefin, which usually contains 4 to 40 carbon atoms, preferably 8 to 36 carbon atoms. Terminal olefins, ie α-olefins, especially those having 12 to 20 carbon atoms are preferred. Mixtures of these olefins are commercially available and such mixtures are contemplated for use in the present invention.

  Two or more co-sulfurized mixtures of these reactants are prepared by reacting a mixture of suitable reactants with a sulfur source. The sulfurized mixture is 10 to 90 parts by weight of reactant (1), or 0.1 to 15 parts by weight of reactant (2); or 10 to 90 parts by weight, often 15 to 60 parts by weight, and more In some cases, 25 to 35 parts by weight of reactant (3) or 10 to 90 parts by weight of reactant (4) can be included. The mixture of the present invention contains reactant (3) and at least one other member of the group of reactants (1), (2) and (4). This sulfurization reaction is generally carried out at a high temperature with stirring and, if necessary, in an inert atmosphere and in the presence of an inert solvent. Sulfiding agents useful in the process of the present invention include elemental sulfur (which is prepared), hydrogen sulfide, sulfur halide + sodium sulfide, and mixtures of hydrogen sulfide with sulfur or sulfur dioxide. Typically, 0.5-3 moles of sulfur are often used per mole of olefinic bonds.

Metal salts (xiv) of alkyl salicylates include calcium salts and other salts of long chain (eg, C ₁₂ -C ₁₆ ) alkyl substituted salicylic acids.

  The amine salt (xv) of alkyl phosphoric acid includes salts of oleyl ester of phosphoric acid and other long chain esters with the following amines. A useful amine in this regard is a tertiary aliphatic primary amine (Primene®). This auxiliary friction modifier can be used in addition to component (a). The amount of this auxiliary friction modifier is generally from 0.1 to 1.5 percent by weight of the lubricating composition, preferably from 0.2 to 1.0 or 0.25 to 0.75 percent. However, in some embodiments, the amount of this auxiliary friction modifier is present at less than 0.2 percent or less than 0.1 weight percent, such as from 0.01 to 0.1 percent. In one embodiment, the amount of dihydroxyethyl taroamine (which is commercially available as ENT-12 ™) is particularly limited to these lower amounts or less.

  The composition of the present invention may also contain a detergent. Detergents used herein include metal salts of organic acids. The organic acid portion of the detergent is a sulfonate, carboxylate, phenate, salicylate. The metal part of the detergent is an alkali metal or alkaline earth metal. Preferred metals include sodium, calcium, potassium and magnesium. Typically, these detergents are overbased, which means that there is a stoichiometric excess of metal over that required to form a neutral metal salt. To do.

  Preferred overbased organic salts include substantially lipophilic sulfonates formed from organic materials. Organic sulfonates are well known materials in the lubricant and detergent arts. The sulfonate compound averages from about 10 to about 40 carbon atoms, preferably from about 12 to about 36 carbon atoms, more preferably from about 14 to about 32 carbon atoms. Should be included. Similarly, these phenates, oxylates and carboxylates are substantially lipophilic.

  In the present invention, these carbon atoms can be in either an aromatic configuration or a paraffinic configuration, but it is preferred to use an alkylated aromatic material. Although naphthalene-based materials can be used, a generally preferred aromatic material is the benzene moiety.

  Therefore, the most preferred composition is an overbased monosulfonated alkylated benzene, preferably a monoalkylated benzene. Typically, the alkyl benzene moiety is obtained from a still bottom source and is mono- or dialkylated. In the present invention, the monoalkylated aromatic material is considered superior to the dialkylated aromatic material in terms of overall properties.

  In the present invention, in order to obtain this monoalkylated salt (benzenesulfonate), it is desirable to use a mixture of monoalkylated aromatic substances (benzene). A mixture in which a substantial portion of the composition contains a polymer of propylene as a starting material for the alkyl group helps the solubility of the salt. The use of monofunctional (eg monosulfonated) materials avoids cross-linking of these molecules while reducing salt precipitation from the lubricant.

  This salt is preferably “overbased”. “Overbased” means that there is a stoichiometric excess of metal over that required to neutralize the anion of the salt. Excess metal resulting from overbasing has the effect of neutralizing the acid that can constitute this lubricant. A second advantage is that this overbased salt increases the coefficient of dynamic friction. Typically, on an equivalent basis, an excess of metal in an amount up to about 30: 1, preferably 5: 1 to 18: 1, in excess of that required to neutralize the anion. Exists.

  The amount of overbased salt used in the lubricating composition is typically about 0.025 to about 3%, preferably 0.1 to 1.0%, on an oil-free basis. . This overbased salt is usually composed in about 50% oil with a TBN range of 10-600 on an oil-free basis. Borated and non-borated overbased detergents are described in U.S. Pat. Nos. 5,403,501 and 4,792,410, the contents of which are hereby incorporated by reference. Incorporated herein by reference.

  The composition of the present invention also includes at least one phosphorus-containing acid, phosphorus-containing acid salt, phosphorus-containing acid ester or derivative thereof (including sulfur-containing analogs) in an amount of 0.002 to 1.0 weight percent. ) Can be contained. These phosphorus-containing acids, phosphorus-containing acid salts, phosphorus-containing acid esters or derivatives thereof include phosphoric acid, phosphorous acid, phosphorus-containing acid esters or salts thereof, phosphorous esters, phosphorus-containing amides, phosphorus-containing carboxyls. Examples include acids or esters, phosphorus-containing ethers, and mixtures thereof.

  In one embodiment, the phosphorus acid, ester or derivative can be an organic or inorganic phosphorus acid, phosphorus acid ester, phosphorus acid salt, or derivative thereof. These phosphorus-containing acids include phosphoric acid, phosphonic acid, phosphinic acid and thiophosphoric acid (including not only monothiophosphoric acid but also dithiophosphoric acid), thiophosphinic acid and thiophosphonic acid. One group of phosphorus-containing compounds is a monoalkyl primary amine salt of an alkyl phosphate represented by the following formula:

ここで、Ｒ^１、Ｒ^２、Ｒ^３は、アルキルまたはヒドロカルビル基であるか、あるいは、Ｒ^１およびＲ^２の１個は、Ｈであり得る。これらの物質は、ジアルキルおよびモノアルキルリン酸エステルの１：１の混合物であり得る。この種の化合物は、米国特許第５，３５４，４８４号で記載されている。

Here, R ¹ , R ² , R ³ can be an alkyl or hydrocarbyl group, or one of R ¹ and R ² can be H. These materials can be a 1: 1 mixture of dialkyl and monoalkyl phosphate esters. This type of compound is described in US Pat. No. 5,354,484.

  85% phosphoric acid is a preferred material to add to a fully formulated composition, which is 0.01 to 0.3 weight percent, preferably 0.00%, based on the weight of the composition. May be included at a level of 03-0.2 or 0.1 weight percent.

  The composition of the present invention can contain other substances as required, provided that the composition complies with the necessary components or specifications. Such materials include antioxidants, including hindered phenol antioxidants, secondary aromatic amine antioxidants, sulfurized phenol antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants. Agents, organic sulfides, disulfides and polysulfides. Other optional ingredients include seal swell compositions (eg, isodecyl sulfolane or phthalate esters), which are designed to keep the seal flexible. Pour point depressants (eg, alkyl naphthalene, polymethacrylate, vinyl acetate / vinyl fumarate or vinyl maleate copolymers, and styrene / maleate copolymers) are also acceptable. Another material is an antiwear agent (eg, zinc dialkyldithiophosphate). These optional materials are known to those skilled in the art and are generally commercially available and are described in further detail in published European Patent Application No. 761,805. Also included are known materials such as corrosion inhibitors, dyes, fluidizing agents, odor masking agents and antifoaming agents. Organoborates and borates can also be included.

  The components can be in the form of a fully formulated lubricant, or in the form of a concentrate within a lesser amount of lubricating oil. If they are present in the concentrate, their concentration is generally directly proportional to their concentration in a more dilute form in the final blend.

  A lubricant formulation is prepared using the following ingredients:

ａ．テレフタル酸（ＴＰＡ）で処理された分散剤であって、これはまた、必要に応じて、ジメルカプトチアジアゾール、無機リン含有酸、および／またはホウ素でも処理されている
ｂ．ＤＭＴＤ＝ジメルカプトチアジアゾール
ｃ．２−エチルヘキシルおよび水素化タロアルキル基を有する第二級アミン
ｄ．通例存在している他の物質（例えば、粘度指数向上剤または消泡剤）を少量で含有し得る。

a. A dispersant treated with terephthalic acid (TPA), which is also optionally treated with dimercaptothiadiazole, an inorganic phosphorus-containing acid, and / or boron b. DMTD = dimercaptothiadiazole c. Secondary amines having 2-ethylhexyl and hydrogenated taroalkyl groups d. Other materials that are commonly present (eg, viscosity index improvers or antifoaming agents) may be included in small amounts.

A specific formulation is prepared and tested as follows:
Formulations are prepared in synthetic base oil blends of 2 and 4 mm ² / s (cSt, 100 ° C.) oils, which are commercially available viscosity index improvers, dispersants, calcium sulfonate detergents, oxidized Contains an inhibitor, a boron-containing friction modifier and a phosphorus-containing friction modifier. To this base oil formulation, in each case, one of the designated amine substances is added.

  The static coefficient of friction of these formulations is reported by μT (ie, the stabilization factor from the SAE # 2 test procedure). A value of μT of at least 0.12 or at least 0.15 (eg, 0.15 to 0.19) is desirable. Average slope of friction versus speed according to the test procedure described in Japan Automobile Standard, JASO M-348-95, “Test Method for Friction Properties of Automatic Transmission Oil” (40 ° C., 24 kg load, 6-11 hour test) Measure. A positive slope over 6-11 hours (eg, a slope higher than 0.0033 or 0.0040) is desirable.

これらの結果は、摩擦調整剤（ａ）を、そのベース調合物に存在している分散剤（ｂ）と併用すると、ＪＡＳＯ ＬＶＦＡスクリーン試験のスロープを正にしつつ、高いレベルの静止摩擦μＴが得られることを示している。

These results show that when friction modifier (a) is used in combination with dispersant (b) present in the base formulation, a high level of static friction μT is obtained while the slope of the JASO LVFA screen test is positive. It is shown that.

  The contents of each reference cited above are incorporated herein by reference. Except for the examples, unless otherwise indicated, all numerical quantities, reaction conditions, molecular weights, carbon atom numbers, etc. in this description that specify the amount of a substance are modified by the term “about”. I understand that Unless otherwise indicated, each chemical or composition referred to herein is considered to be present in its isomers, by-products, derivatives, and other such as would normally be found in commercial grade materials. It should be construed as a commercial grade material that can contain such materials. However, the amount of each chemical component is provided except for solvents or diluent oils that may typically be present in commercial grade materials unless otherwise indicated. Similarly, the range and amount of each element of the invention can be used in combination with the range or amount of any other element. It will be appreciated that the upper and lower amounts, ranges and ratios set forth herein may be combined separately. As used herein, the phrase “consisting essentially” may include substances that do not significantly affect the basic and novel properties of the composition in question.

Claims (17)

A composition suitable for lubricating a transmission, the composition comprising:
(A) a major amount of oil of lubricating viscosity;
(B) Secondary or tertiary amine represented by the following formula: R ¹ R ² NR ³
Wherein R ¹ and R ² are each independently an alkyl group of at least 6 carbon atoms and R ³ is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group; and (C) Dispersant. The composition of claim 1, wherein R ¹ and R ² are each independently an alkyl group of about 8 to about 20 carbon atoms, and R ³ is hydrogen. The composition of claim 1, wherein the secondary or tertiary amine comprises a di-cocoalkylamine. The composition of claim 1, wherein R ³ is —CH ₂ —CHOH—R ⁴ , wherein R ⁴ is hydrogen or an alkyl group. R ⁴ is 1 to about 26 carbon atom alkyl group, A composition according to claim 4. The composition according to claim ⁴ , wherein R ⁴ is methyl. The composition of claim 1, wherein the amine of (b) is represented by the following formula:
R ¹ R ² N—CH ₂ —CHOH—CH ₃
Wherein R ¹ and R ² are each independently an alkyl group of about 8 to about 20 carbon atoms. The composition of claim 6, wherein the amine of (b) comprises a reaction product of a di-cocoalkylamine and propylene oxide. The composition of claim 1 wherein the amount of said amine of (b) is from about 0.01 to about 10 weight percent. The composition of claim 1, wherein the dispersant comprises a succinimide dispersant. The composition of claim 1, wherein the amount of the dispersant is from about 0.3 to about 10 weight percent. The composition of claim 1, further comprising at least one additive selected from the group consisting of detergents, antioxidants, seal swell agents, antiwear agents, and friction modifiers. Furthermore, it contains at least one additive selected from the group consisting of organic borate esters, organic borates, organic phosphorus esters, organic phosphorus salts, inorganic phosphorus-containing acids, and inorganic phosphorus salts. The composition as described. A composition prepared by mixing the ingredients of claim 1. A concentrate for preparing a transmission lubricant by diluting with oil of lubricating viscosity, the concentrate containing:
(A) oil of lubricating viscosity in the amount of concentrate formation;
(B) Secondary or tertiary amine represented by the following formula: R ¹ R ² NR ³
Wherein R ¹ and R ² are each independently an alkyl group of at least 6 carbon atoms and R ³ is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group; and (C) Dispersant. A method of lubricating a transmission, the method comprising supplying to it a lubricant containing:
(A) a major amount of oil of lubricating viscosity;
(B) Secondary or tertiary amine represented by the following formula: R ¹ R ² NR ³
Wherein R ¹ and R ² are each independently an alkyl group of at least 6 carbon atoms and R ³ is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group. . The method of claim 14, wherein the transmission is an automatic transmission.